Interference filter transmission wavelength scanning photometer

ABSTRACT

An interference filter transmission wavelength scanning photometer wherein the angle of inclination of an interference filter ( 3 ) is periodically varied, the wavelength of the light to be transmitted is modulated with the periodical variation centered at the maximum absorption wavelength of the interesting component, the variation of the intensity of the light transmitted through a sample is extracted by an infrared sensor ( 11 ) as an electrical signal. The time between the rise and fall zero cross points of the AC component of the electric signal is determined by a microprocessor ( 16 ), the ratio (T−2T 1 )/T. is calculated from the full period T (time for every other zero cross point of the AC component) and half period T 1  (the time for every zero cross point of the AC component) obtained from the above determined time, and the concentration of the interesting component is determined from the variation of the result of the calculation of the ratio, thereby quantitatively determining the component without interfering of the coexistent components.

FIELD OF THE INVENTION

[0001] The present invention relates to a convenient and cheap analytical apparatus for determining concentration of an interesting component in a sample without interfering of the coexistent components by applying light absorption of the interesting component.

[0002] More particularly, the present invention relates to the convenient and cheap analytical apparatus which is realized by the procedures of:

[0003] preparing an interference filter that has a means scanning transmission wavelength periodically;

[0004] detecting intensity change of light whose wavelengths is scanned by the interference filter and which transmits through the sample;

[0005] determining concentration of the interesting component by examining in period of the detected electric signal.

BACKGROUND OF THE INVENTION

[0006] It is popular to detect a interesting component in a sample or to determine its concentration by applying the light absorption of the interesting component. The simplest method is to measure intensity changes of a monochromatic light transmitting through the sample in which the interesting component absorbing the monochromatic light is contained. For instance, an ultraviolet absorption photometer for monitoring water quality is well-known. This photometer utilizes a phenomenon that an organic waste in water absorbs light of 253.7 nm from a mercury lamp and it consists of a light source, a sample cell, a detector and an amplifier. By this method that is called single beam method, we have often measuring error because an interfering value by the intensity change of the light source is not able to differ from measuring value by the light absorption of the organic waste.

[0007] There is double beam method which removes this defect of the single beam method. In the double beam method, a beam from a light source splits into two beams, that is, one for a sensing beam and other for a reference beam, and the measuring value is obtained as difference or ratio between those intensities. It means that the intensity change of the sensing beam is standardized by the intensity of the reference beam. By adopting the double beam method, the intensity change of the light source does not affect the measuring results.

[0008] Double wavelength spectrometry is another method not to affect the measuring results by the intensity change of the light source. In this method, two different monochromatic beams are alternately transmitted through or reflected on a sample, and absorption intensity of an interesting component in the sample is obtained by measuring difference or ratio between those intensities. Wavelength of the one monochromatic beam for reference is selected different from an absorption wavelength of the interesting component, and wavelength of the other monochromatic beam for sensing is equal to the absorption wavelength of the interesting component, and the intensity change of the monochromatic beam for sensing is standardized by the intensity of the monochromatic beam for reference, therefore, this method has no measuring error by the intensity change of the light source.

[0009] As the present invention is aimed at developing an apparatus which has no measuring error by the intensity change of the light source like the double wavelength spectrometry, a prior art that is one kind of the double wavelength spectrometry will be explained referring FIG. 1.

[0010]FIG. 1 is a block diagram of a filter correlation infrared analyzer, in which infrared beam 121 radiated from an infrared source 101 transmits through a sample cell 102, and an infrared beam after transmitting 122 goes ahead to a modulator 103. The sample cell 102 is a pipe, which is put infrared transmission windows on both ends, and an inlet and an outlet on the near places from the both ends. An interesting component in sample gas flowing through the sample cell absorbs infrared of specific wavelength, and the infrared beam after transmitting 122 loses the energy at the specific wavelength. The modulator 103 is a rotating disk mounting filters, and one of those is a sensing filter 104 whose maximum transmission wavelength is equal to the specific wavelength absorbed by the interesting component, and other is a reference filer 105 whose maximum transmission wavelength is different from the specific wavelength. By rotating the modulator, the filters cross the infrared beam after transmitting 122 periodically. The infrared beam after transmitting 122 is modulated like that the beam transmits through the sensing filter 104 and the reference filter 105 alternately. The modulated infrared beam 123 focuses on an infrared sensor 108 by a focusing lens 107, and is detected as an electric signal. The detected electric signal is amplified by a head amplifier 110, and is put in a synchronous rectifier 111. On the other hand, a synchronous signal detector 106 detects a synchronous signal of the modulator, and puts the synchronous signal in a phase adjuster 109. The phase adjuster adjusts the synchronous signal and puts the signal in the synchronous rectifier 111. The synchronous rectifier 111 rectifies the electric signal synchronizing with the synchronous signal, and obtains measuring signal corresponding to the concentration of the interesting component in the sample.

[0011] By more careful consideration, the gaseous or liquid samples contain many coexisting components with the interesting component. Some of the components interfere to analyze the interesting component, such as water vapor in the case of analyzing nitrogen mono-oxide in flue gas and water or electrolyte in water in the case of analyzing glucose dissolved in water.

[0012] Details about the interfering by the coexisting components will be described referring FIG. 2. A spectrum of interfering components 152 has no peak at an absorption wavelength of the interesting component 153 but tails over it. Even if slope of the tailing is small, the tailing often gives analyzing results fatal errors according to increasing concentration of the interfering components. The double wavelength spectrometry often has problem that the tailing of spectrum of the interfering components gives analyzing results fatal errors, even if reference wavelength 154 is selected near the absorption wavelength of the interesting component 153.

[0013] Then, an objective of the present invention provides an analyzing apparatus which removes the interfering by the tailing spectrum of the interfering components and determines exact concentration of the interesting component by applying the light absorption of the interesting component. It is a further objective of the present invention to provide a convenient and cheap analyzing apparatus measuring non-destructively and non-invasively to a person.

DISCLOSURE OF THE INVENTION

[0014] The present invention provides an interference filter transmission wavelength scanning photometer for determining concentration of an interesting component in a sample without interfering of the coexistent components by applying the light absorption of the interesting component comprising:

[0015] a light source, an interference filter which has means scanning transmission wavelength periodically, an infrared sensor and a zero cross detector.

[0016] The photometer of the present invention can determine concentration of an interesting component in a sample without interfering of the coexistent components by operations comprising the following steps.

[0017] Deciding range of scanning the transmission wavelength of said interference filter, so that center of small change of wavelength induced by scanning the transmission wavelength periodically is equal to an absorption wavelength of said interesting component;

[0018] Detecting intensity of light beam from said light source as an electric signal by said infrared sensor in which light beam is put, after transmitting through said interference filter and transmitting or reflecting on said sample put front or rear of said interference filter;

[0019] Obtaining a full period T (time for every other zero cross point of the AC component) and half period T₁ (time between the rise and fall zero cross point of the AC component) which said zero cross detector takes out of the AC component of said electric signal;

[0020] Determining concentration of said interesting component by calculating a ratio

(T−2T₁)/T.

[0021] Incidentally, a few methods for scanning the transmission wavelength of the interference filter are well-known. One method realizes to scan the transmission wavelength by changing refractive index of spacer layer of gas which pressurizes up and down, keeping displacement between metal layers constant. In other method, displacement between metal layers is changed for scanning the transmission wavelength. Still further method which is suitable for the present invention is one that scans the transmittance wavelength by inclining the normal of the interference filter to the optical axis. The best mode for carrying out the present invention is the interference filter transmission wavelength scanning photometer wherein the transmission wavelength is scanned by swinging the interference filer periodically as inclining the normal of the interference filter to the optical axis.

BRIEF DESCRIPTION OF THE DRAWINGS

[0022]FIG. 1 is a block diagram of a filter correlation infrared analyzer as an example of prior art.

[0023]FIG. 2 is a spectrogram showing a relation between a spectrum of an interesting component and one of interfering components.

[0024]FIG. 3 is a spectrogram showing spectra of an interference filter when inclining its normal to the optical axis;

[0025]FIG. 4 is a chart showing relation between an electrical signal due to an interesting component and one due to interfering components.

[0026]FIG. 5 is a block diagram showing the preferred embodiment of an interference filter transmission wavelength scanning photometer of the present invention.

[0027]FIG. 6 is a sketch illustrating optical sampling system by which an optical signal about concentration of glucose in blood is obtained from human lip.

[0028]FIG. 7 is a spectrogram of main components of which a sample is composed for working example of the present invention.

[0029]FIG. 8 is a correlation plot of measuring values by an interference filter transmission wavelength scanning photometer of the present invention to glucose concentration in human blood measured by a commercial glucose meter.

[0030] Reference signs in drawings are shown bellow.

[0031]1 a light source

[0032]2 a long wavelength pass filter

[0033]3 an interference filter

[0034]4 an axis

[0035]5 S-poles

[0036]6 N-poles

[0037]7 forcing coils

[0038]8 a lens

[0039]9 a quartz rod

[0040]10 a sample

[0041]11 an infrared sensor

[0042]12 an oscillation circuit

[0043]13 a head amplifier

[0044]14 an alternating amplifier

[0045]15 a zero cross detector

[0046]16 a microprocessor

[0047]17 a display device

[0048]18 a key board

[0049]19 a communication port

[0050]31 a quartz rod

[0051]32 a header

[0052]33 an infrared sensor

[0053]34 a human lip

[0054]35 a suction pump

[0055]36 a suction pressure regulator

[0056]101 an infrared source

[0057]102 a sample cell

[0058]103 a modulator

[0059]104 a sensing filter

[0060]105 a reference filter

[0061]106 a synchronous signal detector

[0062]107 a focusing lens

[0063]108 an infrared sensor

[0064]109 a phase adjuster

[0065]110 a head amplifier

[0066]111 a synchronous rectifier

[0067]151 a spectrum of an interesting component

[0068]152 a spectrum of interfering components

[0069]153 an absorption wavelength of an interesting component

[0070]154 a reference wavelength

[0071]161 a short wavelength limit

[0072]162 a long wavelength limit

[0073]163 a high transmittance limit

[0074]164 a low transmittance limit

[0075]165 a transmittance for containing no interesting component

[0076]166 a transmittance for containing an interesting component

[0077]181 an electrical signal due to interfering components

[0078]182 an electrical signal due to an interesting component

[0079]183 an actual observed signal

MOST PREFERABLE EMBODIMENT FOR CARRYING OUT THE INVENTION

[0080] Reference will now be made in detail to the preferred embodiment of the interference filter transmission wavelength scanning photometer of the present invention and the principle for determining concentration of an interesting component as illustrated in the attached drawings.

[0081] In the present invention, an interference filter is swung periodically to incline a normal of the interference filter to an optical axis and thereby, the peak transmission wavelength of the interference filter is scanned in narrow range between a short wavelength limit 161 and a long wavelength limit 162 around an absorption wavelength of an interesting component 153 in a sample as shown in FIG. 2.

[0082] It is well-known that the transmission wavelength is changed by inclining the normal of the interference filter to the optical axis. FIG. 3 shows experimental spectra 171, 172 and 173 of an interference filter which is inclined at the angle of 15, 20 and 25 degree between its normal and the optical axis. And the maximum transmission wavelengths are 2289 nm, 2273 nm and 2257 nm respectively. (Scale of horizontal axis of all spectrogram are linear to wave numbers but all numerical expressions are converted into wavelength for consistent description.)

[0083] Transmittance which is observed after light beam transmits through the sample having a spectrum of interfering components shown in FIG. 2 varies periodically from a high transmittance limit 163 to a low transmittance limit 164, by change of the maximum transmission wavelength from the short wavelength limit 161 at the angle of 25 degree to the long wavelength limit 162 at the angle of 15 degree. An electric signal which is proportional to the intensity of the light beam transmitting through the sample is detected by an infrared sensor, and it is varied periodically like an electric signal due to the interfering component 181 in FIG. 4. It is defined here that the electric signal due to the interfering component 181 takes maximum value to positive when the angle is 25 degree, that is, at the high transmittance limit 163 and minimum value to negative when the angle is 15 degree, that is, at the low transmittance limit 164.

[0084] Continuously, it will be explained to happen when an interesting component in the sample will be increased. By increasing the interesting component, a spectrum of the interesting component 151 in FIG. 2 is enlarged. As enlarging the spectrum 151, transmittance to the wavelength at the center angle between 15 and 25 degree decreases from a transmittance for containing no interesting component 165 to a transmittance for containing the interesting component 166. By decreasing the transmittance, the electrical signal due to the interesting component 182 in FIG. 4 joins in the electric signal due to the interfering components 181, and this electric signal 182 has negative peaks when the electric signal due to the interfering components 181 is in middle between maximum and minimum. After increasing the interesting component, an actual observed signal 183 is synthetic electrical signal which is sum of the electric signal due to the interfering components 181 and the electric signal due to the interesting component 182. The information which has to be obtained is about the amplitude of the electric signal due to the interesting component 182.

[0085] Further explanation about how to obtain the information about the amplitude of the electrical signal due to the interesting component 182 from the actual observed signal 183 will be given the following. The electric signal due to the interfering components is large and is written like the below equation,

F=A sin ωt

[0086] where F is the electrical signal due to the interfering component, A is its amplitude and co is angular frequency which is given like ω=2π/T when T is a full period. As the electric signal due to the interesting component is extremely smaller than the electric signal F, change of the electric signal F can be hardly observed with the joining of the electric signal due to the interesting component. But paying attention to zero cross points which are points when the electric signal F is zero, increase of the amplitude of the electric signal due to the interesting component lets the electric signal F at zero cross points down as a variation of (½)ε, where ε is an amplitude of the electric signal due to the interesting component 182.

[0087] Here, time lags at the zero cross points are estimated when letting the electric signal F at zero cross points down as the variation of (½)ε. The electric signal F is differentiated as the below equation for obtaining slopes of the electric signal F at the zero cross points.

dF/dt=Aω cos ωt

[0088] Slopes at the phase of ωt=π and 2π are −2πA/T and 2πA/T. By letting the electric signal F at the zero cross points down as the variation of (½)ε, the time lags at the zero cross points of the electric signal F are εT/(4πA) fast at the phase of ωt=π and εT/(4πA) slow at the phase of ωt=2π. A time difference between a prolonged half period T₂ and a shortened half period T₁ of the actual observed signal 183 is obtained like shown bellow by above estimation.

T ₂ −T ₁ =εT/(πA)

[0089] Ratio of the time difference to the full period is shown like (T₂−T₁)/T=ε/(πA) and this result shows that the ratio is proportion to the amplitude ε of the electrical signal due to the interesting component 182. This study demonstrates that it is possible to determine concentration of the interesting component without the interfering of coexisting components by examining in the full period (T) and the one half period (T1), as the another half period T₂ can calculate as the difference of the full period T and the one half period T₁.

[0090] Consequently, construction of the interference filter transmission wavelength scanning photometer of the present invention will be explained referring FIG. 5. FIG. 5 is separated two parts, that is, one is a diagram of an optical layout and another is a block diagram of electric circuits. In FIG. 5, shorter wavelengths of the light beam from a light source 1 is cut off by a long wavelength pass filter 2, and longer wavelengths of the light beam passes through the filter and goes ahead to an interference filter 3. The interference filter 3 is fixed with forcing coils 7 and can swing centering an axis 4.S-poles 5 and N-poles 6 of a magnet are installed on the both side of wirings of the forcing coils 7 and by giving the forcing coils 7 alternating current, the interference filter starts to swing centering the axis 4. The angle between the normal of the interference filter and the optical axis is initially set at the angle of 20 degree so that the angle changed by the swinging is within the angle from 15 to 25 degree.

[0091] Modulated light beam by swinging the interference filter focus on an end surface of a quartz rod 9 by a lens 8. The quartz rod 9 guides the light beam near to a sample 10, and the light beam from another end surface of the quartz rod irradiates the sample 10. Part of the light beam reflected on the surface of the sample is put in an infrared sensor 11. The light beam which is modulated by swinging the interference filter and reflected on the sample 10 is detected by the infrared sensor 11 as electric signal. The electric signal is sent to the part of the electric circuits.

[0092] In the part of the electric circuits, an oscillation circuit which supplies alternative current to the forcing coils 7 for swinging the interference filter 3. It is extremely important to keep swinging the interference filter stable because swinging the interference filter forced by the alternative current is origin of all signals. Therefore, a feedback control system is adopted to keep the energy swinging the interference filter constant, measuring the swinging velocity by putting sensing coils at the same position of the forcing coils. The electric signal which is induced in the optical system and detected by the infrared sensor 11 is amplified by head amplifier 13, and its AC component is amplified by an alternative amplifier 14 and put in a zero cross detector 15, having basic frequency decided by the swinging frequency of the interference filter. The zero cross detector generates interrupt signal which informs a microprocessor 16 times when the rising or falling electric signals cross zero level. The microprocessor 16 memorizes the times of every zero cross points by aid of an inner timer. The full period T is obtained as the time from the rising zero cross point to the next rising zero cross point and the half period T₁ as the time from the rising zero cross point to the falling zero cross point. After acquiring data for a certain integrating time, a remainder obtained by subtracting twice value of an integrated half period ΣT₁ from an integrated full period ΣT divided by the integrated full period ΣT gives a ratio that is defined distortion factor here. After concentration of the interesting component (for instance, glucose concentration in blood for glucose meter) has calibrated by using the distortion factors, concentration of the interesting component is determined by the distortion factor and its value is displayed and communicated. A display device 17 which displays concentration value etc., a key board by which the apparatus is operated and a communication port 19 through which many information including the measuring value can be communicated are mounted with the microprocessor.

WORKING EXAMPLE OF THE INVENTION

[0093] Working example of the present invention for determining the concentration of the glucose in the blood will be described in the following.

[0094] The human lip has mass of the capillary blood vessels under the outermost skin, and the red lip is visible to the naked eye. The interference filter transmission wavelength scanning photometer of the present invention is applied for determining the glucose concentration in the blood by diffuse reflectance on this surface. An optical sampling system is shown in FIG. 6. Quartz_rod 31 is the same part signed 9 in FIG. 5. Header 32 holds the quartz rod which guides the light beam to the human lip 34 and an infrared sensor 33 which detects the reflecting light on the human lip 34. A suction pump 35 with a suction pressure regulator 36 sucks a cavity between the human lip 34 and the infrared sensor 33, to stick the surface of the human lip 34 on the header 32.

[0095]FIG. 7 is shown spectra of the main components in the blood, in which a spectrum of water is signed by A, a spectrum of blood paste removed the water from the blood by B and a difference spectrum of the glucose in the water obtained by subtracting the spectrum of the water by C.

[0096] It has been designed in the working example of the present invention that a change of the transmittance of the glucose at the wavelength of 2273 nm (position signed 41) has been adopted for determining the concentration of the glucose in the blood. The maximum transmission wavelength of the interference filter changes from 2289 nm (position signed 42) to 2258 nm (position signed 43), centering 2273 nm. Other specifications for the instrumental design are shown bellow.

[0097] [specifications for the instrumental design] frequency of swinging the interference filter: 150 Hz quartz rod: outer diameter of 1.5 mm length of 160 mm timer clock for measuring period: 8 MHz data integrating time: 300 second clock of microprocessor: 8 MHz

[0098] Depending on above specifications for the instrumental design, a prototype of the interference filter transmission wavelength scanning photometer has been trially manufactured and by using this prototype, the glucose concentration in blood has been determined non-invasively. Data for each data integrating time are divided to ten sections and distortion factors for the sections are calculated. A measuring value for each data integrating time is an average of six medians from ten calculated distortion factors.

[0099] The glucose concentration in the blood of a healthy test person with an empty stomach has been 89 mg/dL measured by a commercial glucose meter. Keeping this condition, the interference filter transmission wavelength scanning photometer of the present invention has been applied for determining the glucose concentration in the blood, and five measuring values have been obtained. Consequently, between 40 minute later and 70 minute later from the time when the test person drank a cup of syrup which was hot water dissolved glucose of 75 g, three measuring values have been obtained. At 60 minute later from the time when the test person drank a cup of the syrup, the glucose concentration in the blood of the test person has been 308 mg/dL measured by the commercial glucosemeter. Assuming that the glucose concentration in the blood of the test person has been regarded as constant between 40 minute later and 70 minute later from the time when the test person drank a cup of the syrup, a correlation plot obtained by these experiments is shown in FIG. 8. It is preferably good result that a coefficient of correlation between the measuring value by the interference filter transmission wavelength scanning photometer of the present invention and the glucose concentration in the blood by the commercial glucose meter is 0.98.

[0100] It has been shown that non-invasive determination of the glucose concentration in the blood is possible with the photometer scanning the transmission wavelength of the interference filter of the present invention.

INDUSTRIAL APPLICABILITY

[0101] Determination of the concentration of the interesting component by applying the light absorption of the material has desirable features such as non-destructive and non-invasive to person. But in many cases, as the tailing of the spectra of coexisting components overlaps the absorption wavelength of the interesting component, it is difficult to determine concentration of the interesting component by using only one wavelength. Therefore many wavelengths are used for the determination, after all a spectrometry is applied for it. Although such a spectrometry has wide application fields, it needs large equipment and expensive cost. With these reasons, the analyzing apparatus by applying the light absorption of the material is desirable, but is not used so commonly. For example, there is no glucose meter by applying the light absorption of the material in Japanese market, although many glucose meters by enzymatic method are commonly used.

[0102] The present invention is able to achieve same performance as the spectrometry for one component in the sample by a simple composition. The present invention is industrially valuable, because picking up a desirable feature for determining the concentration of the interesting component by applying the light absorption of the material, developing to the way to make analytical apparatus good performance to cost, and contributing technically to industrial fields, environmental pollution control, and medical fields. 

1. An interference filter transmission wavelength scanning photometer for determining concentration of an interesting component in a sample without interfering of the coexistent components by applying the light absorption of the interesting component comprising: a light source, an interference filter which has means scanning transmission wavelength periodically, an infrared sensor and a zero cross detector; said photometer having functions to determine concentration of an interesting component in a sample by operations comprising the steps of: deciding range of scanning the transmission wavelength of said interference filter, so that center of small change of wavelength induced by scanning the transmission wavelength periodically is equal to an absorption wavelength of said interesting component; detecting intensity of light beam from said light source as an electric signal by said infrared sensor in which light beam is put, after transmitting through said interference filter and transmitting or reflecting on said sample put front or rear of said interference filter; obtaining a full period T (time for every other zero cross point of the AC component) and half period T₁ (time for every zero cross point of the AC component) which said zero cross detector takes out of the AC component of said electric signal; determining concentration of said interesting component by calculating a ratio (T−2T₁)/T.
 2. The interference filter transmission wavelength scanning photometer according to the claim 1, wherein the transmission wavelength is scanned by swinging an interference filter periodically as inclining the normal of said interference filter to the optical axis. 